Masterbatch with semi-crystalline polyolefin carrier resin

ABSTRACT

A coagent masterbatch comprising a semi-crystalline polyolefin carrier resin and an alkenyl-functional coagent. An electron-beam curable formulation comprising the coagent masterbatch and a polyolefin compound. A method of making the masterbatch and formulation; an electron-beam-cured polyolefin product prepared therefrom; a manufactured article comprising or made from the masterbatch, formulation, or product; and a method of using the manufactured article.

FIELD

Polyolefin compositions, electron beam curing, methods and articles.

INTRODUCTION

Patent publications include CN103865420(A), DE102006017346A1,EP1433811A2, EP2889323A1, US5367030, US6187847B1, US6191230B1,US6936655B2, US20020198335A1, US20080176981A1, US8449801B1. US8691984B2,US9147784B2.

CN103865420(A) to G.-f. Chou, et al. for solar battery plateencapsulating structure. The composition of paragraph [0074] is made bydirect compounding and once made is used directly to make a film. Thecomposition has 110.1 total weight parts and is made from 100 weightparts of an HDPE having melt index (I₂) 0.04 g/10 min., 2 weight parts(1.82 weight percent) of triallyl propyl isocyanuric acid ester, 6weight parts of TiO2, 2 weight parts of vinyltri(beta-methoxyethoxy)silane, and 0.1 weight part of2-hydroxy-4-benzophenone.

DE102006017346A1 to A. a. Nichtnennung for migration stable masterbatch.

EP2889323A1 to S. Deveci et al. for polymer composition comprisingcarbon black and a carrier polymer for the carbon black.

US9147784B2 to Y. Shirahige et al. for sealing material sheet for solarcell module.

A masterbatch is a solid or liquid additive concentrate formulation usedfor conveying an additive into a host polymer in need thereof. Uponbeing cured the host polymer, sometimes called a host resin, base resin,or base polymer, forms a cured product that comprises network polymer ormatrix (e.g., thermoset). The additive may be used to enhance the rateor extent of curing of the host polymer or enhance the performance ofthe cured product. The typical masterbatch comprises the additive and acarrier resin, sometimes called a carrier polymer. The formulation ismade by mixing or blending a smaller amount of the masterbatch with asignificantly larger amount of the host polymer. The concentration ofthe additive in the masterbatch is significantly higher than itsconcentration in the formulation.

Electron-beam irradiation is useful in a method of curing (crosslinking)polyolefins. The method comprises applying a dose of electron-beamirradiation to an (electron beam)-curable (EBC) polyolefin compound togive a cured polyolefin product. The method forms covalent bondsdirectly between polyolefin macromolecules of the EBC polyolefincompound. The electron-beam curing method may be used to cure varioustypes of polyolefins including low density polyethylene (LDPE), linearlow density polyethylene (LLDPE), and high density polyethylene (HDPE).

We introduce problems of: (a) how to improve hot creep (hot set)performance of electron-beam cured polyethylenes, (b) how to increaseelectron-beam irradiation curing of (electron beam)-curable (EBC)polyolefin compounds, and (c) how to make a stable coagent masterbatch.

Crosslinked low density polyethylene (XLDPE) and crosslinked linear lowdensity polyethylene (XLLDPE) are used in various industrialapplications wherein they are exposed to high operating temperatures,such as hot water pipes and insulation layers of electrical powercables. For these applications the crosslinked polyethylenes should haveadequate hot creep (hot set) performance (i.e., retain its shape atoperating temperature). Hot creep performance of (electronbeam)-crosslinked high density polyethylene is usually weaker than thatof (electron beam)-crosslinked linear low density polyethylene. Thus,merely blending a high density polyethylene into a linear low densitypolyethylene followed by electron-beam curing of the blend would not beexpected to improve hot creep performance relative to that of the linearlow density polyethylene alone.

If the dose of electron-beam irradiation is too high, undesirableside-effects occur. These include generating excessive amounts of heat,electrical charges, and/or H₂ gas. Excessive heat can lead to oxidationor deterioration of the cured polyolefin product. Excessive H₂ gas canlead to bubble formation in the cured polyolefin product. Excessiveelectrical charges can lead to electrical discharges from the curedpolyolefin product. If the applied dose is too low, the compound doesnot adequately cure or reach a sufficient cure state (extent of curingor crosslink density), and the performance of the incompletely curedpolyolefin product may be unsuitable for an intended purpose suchprotecting a cable.

Severity of the problems may be attenuated by mixing a minor amount ofcoagent additive into the EBC polyolefin compound to give an (electronbeam)-curable (EBC) formulation comprising the EBC polyolefin compoundand the coagent. The EBC formulation can be cured at a lower dose of theelectron-beam irradiation than the dose used to cure the EBC polyolefincompound without coagent. Also, by virtue of the additional crosslinkingeffect of multivalent crosslinking groups derived from the coagent, theresulting cured polyolefin product can reach an equal or greater curestate than that of a comparative cured polyolefin product preparedwithout the coagent at the same lower EB dose. All other things beingequal, the higher the loading of the coagent in the EBC formulation, thelower the dose of electron-beam irradiation that may be used to achievea given cure state.

The EBC polyolefin compound used as a host polymer in coatings on wireand cable may be a polyethylene such as a low density polyethylene(LDPE) or a linear low density polyethylene (LLDPE). The typical coagentfor these coatings has a polar backbone or substructure to which two ormore alkenyl groups are bonded, such as triallyl isocyanurate (TAIC). Itcan be problematic to store an EBC formulation of the LDPE and/or LLDPE(host polymer) and 0.5 wt% or higher coagent without sweat out ofcoagent at room temperature. The rate and/or extent of sweat out mayworsen with increasing storage time and/or temperature (an elevatedtemperature above room temperature and below the melting temperature ofthe LDPE and/or LLDPE). The more sweat out that occurs, the lesseffective is electron-beam curing of the EBC formulation.

To target higher loadings of coagent in the EBC formulation, porouspolymer pellets may be tried. Porous polymer pellets are commerciallyavailable. For example, Membrana GmbH, Obernburg, Germany, supplyACCUREL XP and ACCUREL MP brands of porous polymer pellets. These porouspolymer pellets are composed of polypropylene, HDPE, LDPE, LLDPE, EVA,EMA, PC, PMMA, PA6, PA12, PS, SBC, SAN, PET, or Bio Polyester, PLA.These porous pellets are said to have an additive loading capacity of upto 50% to 70% depending on the particular product and additive beingloaded.

Problems with porous polymer pellets include limited polymer selectionand leakage of additive from pores of loaded pellets. Problems are moreacute when the additive is a liquid, especially one of low surfacetension and low viscosity at room temperature (23° C. (° C.)). Whenporous polymer pellets are squeezed or compressed, such as when they arebeing loaded with additive or the loaded pellets are being transportedor fed, the squeezing/compressing can push the liquid additive out ofthe pores of the porous polymer pellets. Any resulting product thatcontains or is prepared from the loaded porous polymer pellets may havean insufficient quantity of the additive for its intended use.

SUMMARY

We conceived a technical solution to one, two or more of the introducedproblems of problems of: (a) how to improve hot creep (hot set)performance of electron-beam cured polyethylenes, (b) how to increaseelectron-beam irradiation curing of (electron beam)-curable (EBC)polyolefin compounds, and (c) how to make a stable coagent masterbatch.The technical solution provides an alternative to using porous polymerpellets to carry the coagent and, unlike porous polymer pellets, isunpredictably able to carry high loadings of coagent including a liquidcoagent, such as triallyl isocyanurate, without sweat out during storagethereof. The technical solution comprises a carrier resin that is asemi-crystalline polyolefin. The semi-crystalline polyolefin may besubstantially nonporous and useful for conveying the coagent into an EBCpolyolefin compound (host polymer) such as a LDPE and/or LLDPE.Surprisingly, despite its semi-crystalline, nonporous nature, thesemi-crystalline polyolefin is capable of carrying high loadings of thecoagent, such as up to 20 wt%, and may be more, of TAIC, without sweatout thereof at room temperature during storage or leakage duringhandling comprising compressing or squeezing. Even at elevatedtemperature (above room temperature and below the melting temperature ofthe semi-crystalline polyolefin), the inventive carrier resin may becapable of carrying high loadings of the liquid or solid coagent withoutseepage or leakage thereof.

Without being bound by theory, we believe that the semi-crystallinepolyolefin defines tortuous pathways therein that trap the coagent,releasing the coagent only after the crystalline portion of thesemi-crystalline polyolefin has been melted. Without being bound bytheory, we believe this advantage prevents the coagent from prematurelyflowing out of heated semi-crystalline polyolefin, such as granules orpellets, before they can be fully mixed into a melt of an EBC polyolefincompound (host polymer).

The technical solution enables and includes an inventive coagentmasterbatch that comprises a semi-crystalline polyolefin (carrier resin)containing an alkenyl-functional coagent. Also inventive are an EBCformulation comprising the inventive masterbatch and an EBC polyolefincompound (host polymer); a cured polyolefin product prepared byelectron-beam irradiating the EBC formulation; methods of making andusing same masterbatch, formulation, and product; and articlescontaining or made from same masterbatch, formulation, and product. Webelieve that the cured polyolefin product has both directpolyolefin-polyolefin bonds and polyolefins crosslinked via amultivalent crosslinking group derived from the alkenyl-functionalcoagent.

A formulator can use the inventive masterbatch to quickly make the EBCformulation and a manufacturer can use the EBC formulation to make curedpolyolefin products with fewer defects relative to a comparative EBCpolyolefin compound (host polymer) free of coagent and cured polyolefinproduct made therefrom. Advantageously, the sweat out/leakage stabilityof the inventive coagent masterbatch enables the formulator andmanufacturer to stockpile the coagent masterbatch. It also enables themanufacturer to use coagent masterbatch from the stockpile to make theEBC formulation just prior to electron-beam curing in order to shortenor eliminate the storage of the EBC formulation, thereby avoiding anyrisk of coagent sweat out from the EBC formulation.

DETAILED DESCRIPTION

The Summary and Abstract are incorporated here by reference. Examples ofembodiments include the following numbered aspects.

Aspect 1. A coagent masterbatch comprising (A) a semi-crystallinepolyolefin carrier resin and (B) an alkylene-functional coagent disposedin the (A) semi-crystalline polyolefin carrier resin; wherein (A) is80.0 to 99.9 weight percent (wt%), alternatively 80.0 to 99.0 wt%,alternatively 80.0 to 98.9 wt%, alternatively 84 to 98.9 wt%,alternatively 84 to 98.8 wt%, alternatively 85 to 94 wt%, and (B) isfrom 20.0 to 0.1 wt%, alternatively 20.0 to 1.0 wt%, alternatively 20.0to 1.1 wt%, alternatively 16 to 1.1 wt%, alternatively 16 to 1.2 wt%,alternatively 15 to 6 wt%, respectively, of the combined weight ofconstituents (A) and (B); wherein the (A) semi-crystalline polyolefincarrier resin has a crystallinity of from 55.0 to less than 100 weightpercent (wt%) as measured by Crystallinity Test Method usingdifferential scanning calorimetry (DSC); wherein when the (A)semi-crystalline polyolefin carrier resin is a semi-crystallinepolyethylene, the semi-crystalline polyethylene has a density of greaterthan 0.935 gram per cubic centimeter (g/cm³). The (A) semi-crystallinepolyolefin carrier resin is in a divided solid form such as powder,granules, pellets, or a combination of any two or more thereof. The term“when” above refers to a non-limiting embodiment of the (A)semi-crystalline polyolefin carrier resin. The coagent masterbatchincludes additional embodiments when the (A) semi-crystalline polyolefincarrier resin is not the semi-crystalline polyethylene.

Aspect 2. The coagent masterbatch of aspect 1 characterized by any oneof limitations (i) to (x): (i) the coagent masterbatch is free of (C) an(electron beam)-curable polyolefin compound (host polymer) other thanconstituent (A); (ii) the coagent masterbatch further comprises at leastone additive independently selected from optional additives (D) to (L):(D) a flame retardant, (E) an antioxidant, (F) a processing aid, (G) acolorant, (H) a metal deactivator, (I) an (unsaturated carbon-carbonbond)-free hydrolyzable silane, (J) a corrosion inhibitor, (K) ahindered amine light stabilizer, and (L) an ethylene-based copolymerthat is different than constituents (A) and (C) and is anethylene/(C₄-C₂₀)alpha-olefin copolymer, an ethylene/unsaturatedcarboxylic ester copolymer, or a propylene/ethylene-based copolymer;(iii) the coagent masterbatch does not contain an alkenyl-functionalcoagent-containing porous resin (e.g., a porous LDPE, EVA copolymer, orEEA copolymer powder, granules or pellets having pores containing analkenyl-functional coagent); (iv) the coagent masterbatch does notcontain any porous resin; (v) the coagent masterbatch consists ofconstituents (A) and (B) (i.e., the coagent masterbatch does not containany constituent other than (A) and (B) and the above wt% values for (A)and (B) are of the total weight of the coagent masterbatch (100.00wt%)); (vi) both (i) and (ii); (vii) both (i) and (iii); (viii) both (i)and (iv); (ix) the coagent masterbatch can be maintained for at least 20days at a temperature of 23° C. without sweat out of thealkenyl-functional coagent as measured by Sweat Out Test Method(Quantitative, described later); and (x) both (ix) and any one of (i) to(viii).

Aspect 3. The coagent masterbatch of aspect 1 or 2 wherein the (A)semi-crystalline polyolefin carrier resin comprises, alternativelyconsists essentially of, alternatively consists of any one of (i) to(viii): (i) a semi-crystalline medium density polyethylene; (ii) asemi-crystalline high density polyethylene; (iii) a semi-crystallinepolypropylene; (iv) a semi-crystalline ethylene/propylene copolymer; (v)a semi-crystalline poly(ethylene-co-alpha-olefin) copolymer; (vi) acombination (e.g., mixture or blend) of any two or more of (i), (ii) and(v); (vii) the (A) semi-crystalline polyolefin carrier resin has acrystallinity of 57.5 to < 100 wt%, alternatively 60.0 to < 100 wt%,alternatively 65 to < 100 wt%, alternatively 70.0 to < 100 wt%(Crystallinity Test Method using DSC); or (viii) limitation (vii) andany one of limitations (i) to (vi).

Aspect 4. The coagent masterbatch of any one of aspects 1 to 3 whereinthe (A) semi-crystalline polyolefin carrier resin has any one of (i) to(viii): (i) a density of greater than 0.936 (g/cm³, alternatively atleast 0.940 g/cm³, and is a polyethylene; (ii) a density of 0.89 to0.946 g/cm³, alternatively 0.900 to 0.940 g/cm³, and is a polypropylene;(iii) a crystallinity of 60.0 to < 100 wt%, alternatively 65 to < 100wt%, alternatively 70.0 to < 100 wt%, alternatively 75 to < 100 wt%(Crystallinity Test Method using DSC) and is a polyethylene; (iv) a meltindex (I₂, 190° C./2.16 kg load) of 0.1 to 20 grams per 10 minutes (g/10min.), alternatively 0.2 to 20 g/10 min., alternatively 0.5 to 10 g/10min., all measured according to the Melt Index Test Method (describedlater) and is a polyethylene or a melt flow rate (MFR) of 0.5 to 20 g/10min. (230° C./2.16 kg load) measured according to the Melt Flow RateTest Method (described later) and is a polypropylene; (v) a molecularweight distribution (MWD) that is monomodal; (vi) a MWD that ismultimodal, alternatively bimodal; (vii) wherein the combined weight ofconstituents (A) and (B) is from 50 to 100 wt% alternatively from 70 to100 wt%, alternatively from 80 to 100 wt%, alternatively from 90 to 100wt%, alternatively from 50 to 99.9 wt% alternatively from 70 to 99.9wt%, alternatively from 80 to 99.9 wt%, alternatively from 90 to 99.9wt% of the coagent masterbatch; (viii) any two or limitations (i) to(vii).

Aspect 5. The coagent masterbatch of any one of aspects 1 to 4 whereinthe (B) alkenyl-functional coagent is as described by any one oflimitations (i) to (viii): (i) (B) is 2-allylphenyl allyl ether;4-isopropenyl-2,6-dimethylphenyl allyl ether; 2,6-dimethyl-4-allylphenylallyl ether; 2-methoxy-4-allylphenyl allyl ether; 2,2′-diallyl bisphenolA; O,O′-diallyl bisphenol A; or tetramethyl diallylbisphenol A; (ii) (B)is 2,4-diphenyl-4-methyl-1-pentene or 1,3-diisopropenylbenzene; (iii)(B) is triallyl isocyanurate; triallyl cyanurate; triallyl trimellitate;N,N,N′,N′,N″,N″-hexaallyl-1,3,5-triazine-2,4,6-triamine; triallylorthoformate; pentaerythritol triallyl ether; triallyl citrate; ortriallyl aconitate; (iv) (B) is trimethylolpropane triacrylate,trimethylolpropane trimethylacrylate, ethoxylated bisphenol Adimethacrylate, 1,6-hexanediol diacrylate, pentaerythritoltetraacrylate, dipentaerythritol pentaacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, or propoxylated glyceryl triacrylate; (v) (B)is a polybutadiene having at least 50 wt% 1,2-vinyl content or trivinylcyclohexane; (vi) (B) is an alkenyl-functional organosiloxane of formula(I): [R¹,R²SiO_(2/2)]_(n) (I), wherein subscript n is an integer greaterthan or equal to 3; each R¹ is independently a (C₂-C₄)alkenyl or aH₂C═C(R^(1a))—C(═O)—O—(CH₂)_(m)— wherein R^(1a) is H or methyl andsubscript m is an integer from 1 to 4; and each R² is independently H,(C₁-C₄)alkyl, phenyl, or R¹; (vii) (B) is an alkenyl-functionalmonocyclic organosiloxane of formula (II): (R¹)_(x)Si(OR²)(_(4-x)) (II),wherein subscript x is an integer from 0 to 4; each R¹ is independentlya (C₂-C₄)alkenyl or a H₂C═C(R¹ ^(a))—C(═O)—O—(CH₂)_(m)— wherein R^(1a)is H or methyl and subscript m is an integer from 1 to 4; and each R² isindependently H, (C₁-C₄)alkyl, phenyl, or R¹; with the proviso that thealkenyl-functional monocyclic organosiloxane of formula (II) containsfrom 2 to 4 R¹ groups; (viii) a combination or any two or more of (i) to(vii).

Aspect 6. A method of storing a coagent masterbatch, the methodcomprising maintaining for at least 20 days the coagent masterbatch ofany one of aspects 1 to 5 at a temperature from 20° to 25° C. to give astored coagent masterbatch without sweat out of the alkenyl-functionalcoagent as measured by Sweat Out Test Method (Quantitative, describedlater).

Aspect 7. An (electron beam)-curable formulation comprising the coagentmasterbatch of any one of aspects 1 to 5, or the stored coagentmasterbatch made by the method of aspect 6, and (C) an electron-beamcurable (EBC) polyolefin compound.

Aspect 8. The (electron beam)-curable formulation of aspect 7characterized by any one of limitations (i) to (xiii): (i) the (C) EBCpolyolefin compound is a low density polyethylene (LDPE) having adensity from 0.910 to 0.925 g/cm³; (ii) the (C) EBC polyolefin compoundis a linear low density polyethylene (LLDPE) having a density from 0.910to 0.925 g/cm³; (iii) the (C) EBC polyolefin compound is a mediumdensity polyethylene (MDPE) having a density from 0.926 to 0.940 g/cm³;(iv) the (C) EBC polyolefin compound is a high density polyethylene(HDPE) having a density from 0.941 to 0.990 g/cm³; (v) the (C) EBCpolyolefin compound is a polyethylene elastomer selected from elastomersbased on ethylene copolymers such as an ethylene-propylene rubber (EPR),an ethylene-1-butene rubber (EBR), and an ethylene-1-octene rubber(EOR); (vi) the (C) EBC polyolefin compound is anethylene/(C₃-C20)alpha-olefin) copolymer; (vii) the (C) EBC polyolefincompound is an ethylene-propylene copolymer (EPP); (viii) the (C) EBCpolyolefin compound is an ethylene-propylene-diene monomer (EPDM)copolymer; (ix) the (C) EBC polyolefin compound is a combination of anytwo or more of (i) to (viii); (x) the (electron beam)-curableformulation further comprises at least one additive that is not aconstituent of the coagent masterbatch and is independently selectedfrom optional additives (D) to (L): (D) a flame retardant, (E) anantioxidant, (F) a processing aid, (G) a colorant, (H) a metaldeactivator, (I) an (unsaturated carbon-carbon bond)-free hydrolyzablesilane, (J) a corrosion inhibitor, (K) a hindered amine lightstabilizer, and (L) an ethylene-based copolymer additive that isdifferent than constituents (A) and (C) and is anethylene/(C₄-C₂₀)alpha-olefin copolymer, an ethylene/unsaturatedcarboxylic ester copolymer, or a propylene/ethylene-based copolymer;(xi) limitation (x) and any one of limitations (i) to (viii); (xii) (B)is from 0.1 to 20 wt%, alternatively 0.5 to 15 wt%, alternatively 5 to15 wt%, alternatively 5 to 14 wt% of the combined weight of constituents(A), (B) and (C); and (xiii) limitation (xii) and any one of limitations(i) to (xi).

Aspect 9. A method of making an (electron beam)-curable formulation, themethod comprising mixing together a divided solid form of the coagentmasterbatch of any one of aspects 1 to 5, or the stored coagentmasterbatch made by the method of aspect 6, and a (C) EBC polyolefincompound in divided solid or melt form so as to give a mixture; and meltmixing or extruding the mixture so as to make the (electronbeam)-curable (EBC) formulation. In some aspects the EBC formulationthat is made is the EBC formulation of aspect 8. The extruded EBCformulation may be pelletized to give the EBC formulation as solidpellets. Alternatively, the extruded EBC formulation may be cooled togive the EBC formulation as a shaped solid such as an insulation layeron a cable.

Aspect 10. A method of electron-beam curing a formulation in needthereof, the method comprising irradiating the EBC formulation of aspect7 or 8, or the (electron beam)-curable formulation made by the method ofaspect 9, with an effective dose of electron-beam irradiation so as togive an electron-beam cured polyolefin product. In some aspects coagentmasterbatch is the stored coagent masterbatch made by the method ofaspect 6. In some aspects the method further comprises a preliminarystep before the irradiating step of maintaining for from 1 to 100 days,alternatively from 5 to 50 days, alternatively from 14 to 20 days thecoagent masterbatch of any one of aspects 1 to 5 at a temperature from20° to 25° C. to give a stored coagent masterbatch without sweat out ofthe alkenyl-functional coagent as measured by Sweat Out Test Method(described later), wherein the coagent masterbatch of the EBCformulation comprises the stored coagent masterbatch. The EBCformulation in a shaped solid form may be cured by the method to give ashaped form of the electron-beam-cured polyolefin product.

Aspect 11. An electron-beam-cured polyolefin product made by the methodof aspect 10. The product may have a defined shape such as a coating,film, or molded or extruded shape.

Aspect 12. A manufactured article comprising the electron-beam-curedpolyolefin product of aspect 11 and a component in operative contacttherewith.

Aspect 13. A coated conductor comprising a conductive core and apolymeric layer at least partially surrounding the conductive core,wherein at least a portion of the polymeric layer comprises theelectron-beam-cured polyolefin product of aspect 11.

Aspect 14. A method of conducting electricity, the method comprisingapplying a voltage across the conductive core of the coated conductor ofaspect 13 so as to generate a flow of electricity through the conductivecore.

Additive: a solid or liquid compound or substance that imparts a desiredproperty to a host polymer, or to a formulation comprising a masterbatchand host polymer, or to a reaction product prepared therefrom. Theproperty may be a chemical, electrical, mechanical, optical, physical,and/or thermal property.

Alpha-olefin: a compound of formula (I): H₂C═C(H)—R (I), wherein R is astraight chain alkyl group.

Carrier resin: a divided solid (particulate) polymer used fortemporarily holding and later releasing an additive.

Coagent: a multifunctional compound that enhances crosslinking of(co)polymer macromolecules during a curing method. A single coagentmolecule may react with two, three, or more (co)polymer macromoleculesto make crosslinked (co)polymer macromolecular products wherein two,three, or more of the (co)polymer macromolecules have been covalentlybonded to a same multivalent crosslinking group derived from the coagentmolecule. Coagent is also known as a curing coagent or crosslinkingcogent. Typical coagents are acyclic or cyclic compounds that containcarbon atoms or silicon atoms in their respective backbone or ringsubstructure. Thus, the backbone or ring substructure of a coagent isbased on carbon (carbon-based substructure) or silicon (silicon-basedsubstructure). Coagent is different in structure and function than acure agent.

Coagent masterbatch: A masterbatch wherein the additive comprises acoagent. The coagent masterbatch may contain at least 45 wt%,alternatively at least 50 wt%, alternatively at least 55 wt%,alternatively at least 70 wt%, alternatively at least 80 wt%,alternatively at least 90 wt% of the (A) semi-crystalline polyolefincarrier resin; all based on total weight of the coagent masterbatch. Thecoagent masterbatch may contain from 55 to 1 wt%, alternatively 50 to 1wt%, alternatively 45 to 1 wt%, alternatively 30 to 1 wt%, alternatively20 to 1 wt%, alternatively 10 to 1 wt% of the (B) alkenyl-functionalcoagent. The coagent masterbatch may be free of: (i) an ethylene/silanecopolymer, (ii) an ethylene/vinyl acetate (EVA) copolymer, (iii) anethylene/alkyl acrylate copolymer (e.g., EEA copolymer), (iv) carbonblack; (v) a pigment or colorant; (vi) a filler; (vii) any two,alternatively any six of (i) to (vi). The coagent masterbatch may havefrom > 0 to 5 wt% of any other carrier resin such as a low densitypolyethylene (LDPE), a linear low density polyethylene (LLDPE), anethylene/alpha-olefin copolymer, an EEA copolymer, a polypropylene, anylon (e.g., Nylon 6 or 66), a BPA-PC, a polycarbonate, a BPA-PS, apolysulfone, or a polyphenylene oxide; alternatively the coagentmasterbatch may be free of any carrier resin, or any resin, other thanthe (A) semi-crystalline polyolefin carrier resin. The coagentmasterbatch may further comprise a filler. The filler may be calciumcarbonate, zinc borate, zinc molybdate, zinc sulfide, carbon black,talc, magnesium oxide, zinc oxide, or a clay. The coagent masterbatchmay be free of any additive that prevents electron-beam curing of thehost polymer.

Coated conductor: a material for conducting electricity at leastpartially covered by a layer of a protective material. An example is anelectrical power cable.

Comonomer composition distribution (CCD) or chemical compositiondistribution is the variability of the amounts of comonomeric unitsincorporated into copolymer macromolecules. When the amount ofcomonomeric units incorporated vary over a wide range from copolymermacromolecule to copolymer macromolecule, the CCD is said to be “broad”.When the amount of comonomeric units incorporated into the copolymermacromolecules is relatively consistent from copolymer macromolecule tocopolymer macromolecule, the CCD is said to be “narrow”. A measurementof CCD is comonomer distribution breadth index (CDBI).

Comonomer distribution breadth index (CDBI) is the weight percent (wt%)of copolymer molecules having a comonomeric unit content within 50percent (i.e., ± 50%) of the median total molar comonomeric unitcontent. Such a relatively high CDBI value indicates that the copolymermolecules are relatively uniform in comonomeric unit content. The CDBIvalue of a linear polyethylene homopolymer, which does not contain acomonomer, is defined to be 100%. When a CDBI value for a firstcopolymer is higher than that of a second copolymer, the higher CDBIvalue indicates that the comonomer distribution of the first copolymeris more controlled or limited than the comonomer distribution of thesecond copolymer.

(Co)polymer: polymer (homopolymer) and/or copolymer. A homopolymer is amacromolecule composed of monomeric units derived from only one monomerand no comonomer units. A copolymer is a macromolecule or collection ofmacromolecules having monomeric units and one or more different types ofcomonomeric units, wherein the monomeric units comprise on average permolecule a majority of the total units. The copolymer’s monomeric unitsare made by polymerizing a first monomer and the one or more differenttypes of comonomeric units are made by polymerizing one or moredifferent second or more monomers, referred to as comonomers. Monomersand comonomers are polymerizable molecules. A monomeric unit, alsocalled a monomer unit or “mer”, is the largest constitutional unitcontributed by (derived from) a single monomer molecule to the structureof the macromolecule(s). A comonomeric unit, also called a comonomerunit or “comer”, is the largest constitutional unit contributed by(derived from) a single comonomer molecule to the structure of themacromolecule(s). Each unit is typically divalent (prior to any curingor crosslinking). A “bipolymer” is a copolymer made from a monomer(e.g., ethylene) and one type of comonomer (e.g., 1-hexene). A“terpolymer” is a copolymer made from a monomer (e.g., ethylene) and twodifferent types of comonomers (e.g., propylene and 1,3-butadiene). Anethylenic-based copolymer has 50 to less than 100 wt% monomeric unitsderived from ethylene (CH₂═CH₂) and from greater than 0 to 50 wt%comonomeric units derived from one or more comonomers. A propylene-basedcopolymer has 50 to less than 100 wt% monomeric units derived frompropylene (CH₂═CH₂CH₃) and from greater than 0 to 50 wt% comonomericunits derived from one or more comonomers (e.g., ethylene, butadiene).

Cure agent: a radical-generating compound (in situ) that upon activationforms a free-radical and initiates or enhances reactions involvingcrosslinking of macromolecules. Activation of the cure agent may beachieved by subjecting the cure agent to heat or light. Examples of cureagents are peroxides, diazo-functional organic compounds, and2,3-dimethyl-2,3-diphenylbutane. Examples of peroxides arehydrogen-organic peroxides of formula H—O—O—R and organic peroxides offormula R—O—O—R, wherein each R is independently a hydrocarbyl group.

Curing: crosslinking to form a crosslinked product (network polymer).

Day: any consecutive 24 hour period.

Divided solid: a particulate material in a state of matter characterizedby relatively stable shape and volume. Examples are powers, granules,and pellets.

Effective dose: a quantity sufficient to result in crosslinking of apolyolefin in need thereof and receiving the quantity.

Electron-beam curable: capable of being cured by irradiation (treatment)with high-energy beta radiation such as from a high-energy electron-beamaccelerator. The irradiation induces covalent bonding (crosslinking)between adjacent macromolecules to form a network polymer.

High density polyethylene (HDPE): having a density from 0.941 to 0.990g/cm³, an alpha-olefin comonomeric unit content greater than 0 wt%, andshort chain branching.

Linear low density polyethylene (LLDPE): having density from 0.910 to0.925 g/cm³, an alpha-olefin comonomeric unit content greater than 0wt%, and short chain branching. The LLDPE may have a comonomerdistribution breadth index (CDBI) of from 70 to less than 100 weightpercent.

Low density polyethylene (LDPE): a polyethylene homopolymer (0 wt%comonomeric unit content, CDBI = 100%, free of short-chain branching)having density from 0.910 to 0.925 g/cm³. LDPE may be made viafree-radical polymerization mechanism in a catalyst-free, high pressurepolymerization process.

Medium density polyethylene (MDPE): having a density from 0.926 to 0.940g/cm³.

Manufactured article: man-made (by hand or machine) thing.

Masterbatch: see Introduction.

Melt: a liquid formed by heating a solid material above its highestmelting temperature.

Polyolefin: a macromolecule, or collection of macromolecules, composedof constitutional units derived from polymerizable olefins.

Semi-crystalline: a solid material having a first region that is neithercrystalline nor amorphous and a second region that is amorphous. Havinga percent crystallinity, typically between 10% and 90%, as measured bythe Crystallinity Test Method described later.

Shaped solid: a state of matter of relatively constant volume andexternal form, which is man-made (by hand or machine). E.g., extruding,molding, or coating a fluid into the external form, followed by coolingthe external form in place to give a shaped solid.

Storing: keeping or maintaining.

Sweat out: slow release of a liquid from a solid material containing theliquid therein.

The coagent masterbatch, EBC formulation, and cured polyolefin productmay be referred to herein as the inventive masterbatch, formulation, andproduct, respectively.

The inventive masterbatch, formulation, and/or product may be free of anadditive that is an acid condensation catalyst. Examples of the acidcondensation catalyst are (i) an organosulfonic acid, anorganophosphonic acid, or a hydrogen halide; (ii) an organosulfonicacid; (iii) an alkyl-substituted arylsulfonic acid; (iv) analkyl-substituted arylsulfonic acid wherein there is/are 1 or 2(C₅-C₂₀)alkyl substituent(s) and 1 aryl group that is phenyl ornaphthyl; (v) a (C₁-C₅)alkylphosphonic acid, wherein the (C₁-C₅)alkyl isunsubstituted or substituted with one —NH₂ group; (vi) HF, HCl, or HBr;(vii) a Lewis acid; or (viii) a combination of any two or more of (i) to(vii).

The inventive masterbatch, formulation, and/or product may be free ofTiO₂. The inventive masterbatch and/or formulation may have greater thanor equal to 2.0 weight percent of coagent, may have a MI greater than orequal to 0.1 g/10 minutes, or a combination of any two or more thereof.The inventive masterbatch, formulation, and/or product may be free of acure agent such as a peroxide such as a hydrogen-organic peroxide or anorganic peroxide.

Coagent masterbatch. In some aspects the coagent masterbatch is adivided solid such as a powder, granules and/or pellets.

Electron-beam curable formulation. The total weight of all constituentsand additives in the inventive masterbatch, formulation, and productindependently is 100.00 wt%. The electron-beam curable formulation maybe a one-part formulation, alternatively a two-part formulation. Thetwo-part formulation may comprise first and second parts, wherein thefirst part consists essentially of the coagent masterbatch and thesecond part consists essentially of the (C) EBC polyolefin compound.

Constituent (A) semi-crystalline polyolefin carrier resin. Thesemi-crystalline polyolefin carrier resin may be a semi-crystallinepolyethylene that is a semi-crystalline medium density polyethylene(MDPE), a semi-crystalline high density polyethylene (HDPE), or acombination thereof. Constituent (A) semi-crystalline polyolefin carrierresin may be in any divided solid form such as powder, granules,pellets, or a combination of any two or more thereof.

The semi-crystalline HDPE may have a maximum density of 0.970 g/cm³,alternatively at most 0.960 g/cm³, alternatively at most 0.950 g/cm³.The semi-crystalline HDPE may have a density of from > 0.935 to 0.970g/cm³, alternatively 0.935 to 0.965 g/cm³. The density of the (A) may bemeasured by ASTM D-1505, Test Method for Density of Plastics by theDensity-Gradient Technique.

The (A) semi-crystalline polyolefin carrier resin may have acrystallinity of at least 55 wt%, alternatively at least 58 wt%,alternatively at least 59 wt%. In any one of the immediately precedingaspects the crystallinity may be at most 90 wt%, alternatively at most80 wt%, alternatively at most 78 wt%. In some aspects the crystallinityis from 55 to 80 wt%, alternatively from 58 to 78 wt%, alternativelyfrom 58 to 76 wt%, alternatively from 62 to 78 wt%, alternatively anyone of 59 ± 1 wt%, 62 ± 1 wt%, 76 ± 1 wt%, and 77 ± 1 wt%. Thecrystallinity of a semi-crystalline polyolefin resin, such as (A)semi-crystalline polyolefin carrier resin, may be determined bydifferential scanning calorimetry (DSC) according to ASTM D3418-15 orthe Crystallinity Test Method using DSC described later. For asemi-crystalline polyethylene resin, wt% crystallinity =(ΔH_(f)*100%)/292 J/g. For a semi-crystalline polypropylene resin, wt%crystallinity = (ΔH_(f)*100%)/165 J/g. In the respective equationsΔH_(f) is the second heating curve heat of fusion for the polyethyleneresin or polypropylene resin, as the case may be, * indicatesmathematical multiplication, / indicates mathematical division, 292 J/gis a literature value of the heat of fusion (ΔH_(f)) for a 100%crystalline polyethylene, and 165 J/g is a literature value of the heatof fusion (ΔH_(f)) for a 100% crystalline polypropylene. Preferably,crystallinity is determined by DSC according to the Crystallinity TestMethod described later.

The (A) semi-crystalline polyolefin carrier resin may have a melt index(I₂, 190° C./2.16 kg load) of 10 to 20 g/10 min., alternatively 0.1 to10 g/10 min., alternatively 0.20 to 9 g/10 min. The I₂ may be determinedby ASTM D1238 as described later.

The (A) semi-crystalline polyolefin carrier resin may be characterizedby a molecular weight distribution (MWD) that is monomodal,alternatively bimodal.

The (A) semi-crystalline polyolefin carrier resin may be asemi-crystalline HDPE that is bimodal and has a density of from 0.950 to0.958 g/cm³ and a melt index of from 0.20 to 0.40 g/10 min. The (A)semi-crystalline polyolefin carrier resin may be a semi-crystalline HDPEthat is monomodal and has a density of from 0.930 to 0.970 g/cm³ and amelt index of from 0.65 to 9 g/10 min., alternatively a density from0.935 to 0.965 g/cm³ and a melt index from 0.7 to 8.5 g/10 min.

Constituent (B) alkenyl-functional coagent. A molecule that contains abackbone or ring substructure and two or more propenyl, acrylate, and/orvinyl groups bonded thereto, or a collection of such molecules. In someaspects the backbone or substructure is composed of carbon atoms andoptionally nitrogen atoms and is free of silicon atoms. In some aspectsthe backbone or substructure is composed of silicon atoms and optionallyoxygen atoms.

When the backbone or substructure of (B) alkenyl-functional coagent iscomposed of carbon atoms and optionally nitrogen atoms and is free ofsilicon atoms, the (B) may be a propenyl-functional coagent as describedby any one of limitations (i) to (v), a vinyl-functional coagent asdescribed by any one of limitations (vi) to (vii), or a combinationthereof as described in limitation (viii): (i) (B) is 2-allylphenylallyl ether; 4-isopropenyl-2,6-dimethylphenyl allyl ether;2,6-dimethyl-4-allylphenyl allyl ether; 2-methoxy-4-allylphenyl allylether; 2,2′-diallyl bisphenol A; O,O′-diallyl bisphenol A; ortetramethyl diallylbisphenol A; (ii) (B) is2,4-diphenyl-4-methyl-1-pentene or 1,3-diisopropenylbenzene; (iii) (B)is triallyl isocyanurate (“TAIC”); triallyl cyanurate (“TAC”); triallyltrimellitate (“TATM”);N,N,N′,N′,N″,N″-hexaallyl-1,3,5-triazine-2,4,6-triamine (“HATATA”; alsoknown as N²,N²,N⁴,N⁴,N⁶,N⁶-hexaallyl-1,3,5-triazine-2,4,6-triamine);triallyl orthoformate; pentaerythritol triallyl ether; triallyl citrate;or triallyl aconitate; (iv) (B) is a mixture of any two of thepropenyl-functional coagents in (i). Alternatively, the (B) may be anacrylate-functional conventional coagent selected fromtrimethylolpropane triacrylate (“TMPTA”), trimethylolpropanetrimethylacrylate (“TMPTMA”), ethoxylated bisphenol A dimethacrylate,1,6-hexanediol diacrylate, pentaerythritol tetraacrylate,dipentaerythritol pentaacrylate, tris(2-hydroxyethyl) isocyanuratetriacrylate, and propoxylated glyceryl triacrylate; (vi) polybutadienehaving at least 50 wt% 1,2-vinyl content; (vii) trivinyl cyclohexane(“TVCH”) (viii) a combination or any two or more of the foregoingcoagents. Alternatively, the (B) may be a coagent described in US5,346,961 or US 4,018,852. In some aspects the (B) is thepropenyl-functional coagent as described by any one of limitations (i)to (v). In some aspects the (B) is the propenyl-functional coagentselected from TAIC, TAC, TATM, HATATA, TMPTA, and TMPTMA; alternativelyTAIC, TAC, and TMPTMA; alternatively TAIC; alternatively TAC;alternatively TATM; alternatively HATATA; alternatively TMPTA;alternatively TMPTMA.

When the backbone of substructure of (B) alkenyl-functional coagent iscomposed of silicon atoms and optionally oxygen atoms, the (B) may be analkenyl-functional organosiloxane of any one of limitations (i) to (iv):(i) a monocyclic organosiloxane of formula (I): [R¹,R²SiO_(2/2)]_(n)(I), wherein subscript n is an integer greater than or equal to 3; eachR¹ is independently a (C₂-C₄)alkenyl or aH₂C═C(R^(1a))—C(═O)—O—(CH₂)_(m)— wherein R^(1a) is H or methyl andsubscript m is an integer from 1 to 4; and each R² is independently H,(C₁-C₄)alkyl, phenyl, or R¹, wherein in some aspects the coagentmasterbatch is free of (i.e., lacks) a phosphazene base; (ii) analkenyl-functional monocyclic organosiloxane of formula (II):(R¹)xSi(OR²)_((4-x)) (II), wherein subscript x is an integer from 0 to4; each R¹ is independently a (C₂-C₄)alkenyl or aH₂C═C(R^(1a))—C(═O)—O—(CH₂)_(m)— wherein R^(1a) is H or methyl andsubscript m is an integer from 1 to 4; and each R² is independently H,(C₁-C₄)alkyl, phenyl, or R¹; with the proviso that thealkenyl-functional monocyclic organosiloxane of formula (II) containsfrom 2 to 4, alternatively 2 or 3, alternatively 3 or 4, alternatively2, alternatively 3, alternatively 4 R¹ groups. In some aspects the (B)is the monocyclic organosiloxane of formula (I). In some aspects the (B)is the monocyclic organosiloxane of formula (I), wherein subscript n isan integer 3 or 4; each R¹ is independently a (C₂-C₄)alkenyl; and eachR² is (C₁-C₄)alkyl. In some aspects the (B) is the monocyclicorganosiloxane of formula (I), wherein subscript n is an integer 3 or 4;each R¹ is independently a (C₂-C₄)alkenyl; and each R² is (C₁-C₄)alkyl.In some aspects the (B) is the monocyclic organosiloxane of formula (I),wherein subscript n is an integer 3 or 4; each R¹ is independently a(C₂)alkenyl (i.e., vinyl); and each R² is methyl.

In some aspects the (B) is the propenyl-functional coagent or themonocyclic organosiloxane of formula (I). In some aspects thepropenyl-functional coagent is selected from TAIC, TAC, TATM, HATATA,TMPTA, and TMPTMA; alternatively TAIC, TAC, and TMPTMA; alternativelyTAIC; alternatively TAC; alternatively TATM; alternatively HATATA;alternatively TMPTA; alternatively TMPTMA; and the monocyclicorganosiloxane of formula (I) is selected from the monocyclicorganosiloxane of formula (I), wherein subscript n is an integer 3 or 4;each R¹ is independently a (C₂-C₄)alkenyl; and each R² is (C₁-C₄)alkyl;alternatively the monocyclic organosiloxane of formula (I), whereinsubscript n is an integer 3 or 4; each R¹ is independently a(C₂)alkenyl; and each R² is methyl.

Constituent (C) electron-beam curable (EBC) polyolefin compound (“HostPolymer”). The (C) EBC polyolefin compound may be a low densitypolyethylene (LDPE, linear low density polyethylene (LLDPE), mediumdensity polyethylene (MDPE), high density polyethylene (HDPE), apolyolefin elastomer, an ethylene/(C₃-C₄₀)alpha-olefin) copolymer, or acombination (e.g., blend or melt mixture) of any two or more thereof.The LDPE may have a density from 0.910 to 0.925 g/cm³. The LLDPE mayhave a density from 0.910 to 0.925 g/cm³. The MDPE may have a densityfrom 0.926 to 0.940 g/cm³. The HDPE may have a density from 0.941 to0.990 g/cm³. The elastomers based on ethylene copolymers may be selectedfrom the EPR and EBR, alternatively the EPR and EOR, alternatively theEBR and EOR, alternatively EPR, alternatively EBR, alternatively EOR.Examples of such elastomers are ENGAGE™, AFFINITY™, and INFUSE™polyolefin elastomers available from The Dow Chemical Company. Theethylene/(C₃-C₂₀)alpha-olefin) copolymer may be an ethylene/propylenecopolymer or an ethylene/(C₄-C₂₀)alpha-olefin) copolymer as describedherein. The ethylene-propylene copolymer (EPP) may be a bipolymer or anethylene-propylene-diene monomer (EPDM) copolymer. The (C) EBCpolyolefin compound may be different than the (A) semi-crystallinepolyolefin carrier resin and the (L) ethylene-based polymer additive inat least one characteristic selected from monomer composition, comonomercomposition, density, crystallinity, melt index, melt flow rate,number-average molecular weight (M_(n)), weight-average molecular weight(M_(w)), molecular weight distribution (M_(w)/M_(n)), and porosity.

Prior to the mixing step used to prepare the EBC formulation, the (C)EBC polyolefin compound may be in a divided solid form such as a powder,granules and/or pellets.

Optional constituent (additive) (D) flame retardant. The (D) flameretardant is a compound that inhibits or delays the spread of fire bysuppressing chemical reactions in a flame. In some aspects (D) flameretardant is (D1) a mineral, (D2) an organohalogen compound, (D3) an(organo)phosphorous compound; (D4) a halogenated silicone; or (D5) acombination of any two or more of (D1) to (D4). In some aspects (D) isnot present in the inventive masterbatch, formulation, and/or product.In some aspects (D) is present in the inventive masterbatch,formulation, and/or product at a concentration from 0.1 to 20 wt%,alternatively 1 to 10 wt%; and alternatively 5 to 20 wt%; all based ontotal weight thereof.

Optional constituent (additive) (E) antioxidant. A compound forinhibiting oxidation of a polyolefin. Examples of suitable secondantioxidants are polymerized 1,2-dihydro-2,2,4-trimethylquinoline(Agerite MA);tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione(Cyanox 1790); distearyl-3,3-thiodiproprionate (DSTDP);tetrakismethylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) methane(Irganox 1010);1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine (Irganox1024); bis(4,6-dimethylphenyl)isobutylidene (Lowinox 22IB46); and4,4-thiobis(2-tert-butyl-5-methylphenol) (TBM6). In some aspects (E) isnot present in the inventive masterbatch, formulation, and/or product.In some aspects (E) is present in the inventive masterbatch,formulation, and/or product at a concentration of from 0.01 to 10 wt%,alternatively 0.05 to 5 wt%, alternatively 0.1 to 3 wt%, based on totalweight thereof.

Optional constituent (additive) (F) processing aid. Constituent (F) mayimprove flow of a melt of the coagent masterbatch through a machine. (F)may be an organic processing aid such as a fluoropolymer or a siliconeprocessing aid such as a polyorganosiloxane or fluoro-functionalizedpolyorganosiloxane. In some aspects (F) is not present in the inventivemasterbatch, formulation, and/or product. In some aspects (F) is presentin the inventive masterbatch, formulation, and/or product at aconcentration of from 1 to 20 wt%, alternatively 2 to 18 wt%,alternatively 3 to 15 wt%, based on total weight thereof.

Optional constituent (additive) (G) a colorant. E.g., a pigment or dye.E.g., carbon black or titanium dioxide. The carbon black may be providedas a carbon black masterbatch that is a formulation ofpoly(1-butene-co-ethylene) copolymer (from ≥ 95 wt% to < 100 wt% of thetotal weight of the masterbatch) and carbon black (from > 0 wt% to ≤ 5wt% of the total weight of the carbon black masterbatch. In some aspects(G) is not present in the inventive masterbatch, formulation, and/orproduct. In some aspects (G) colorant is present in the inventivemasterbatch, formulation, and/or product at from 0.1 to 35 wt%,alternatively 1 to 10 wt%, based on total weight thereof.

Optional constituent (additive) (H) a metal deactivator. E.g., oxaylylbis(benzylidene hydrazide) (OABH). In some aspects (H) is not present inthe inventive masterbatch, formulation, and/or product. In some aspects(H) is present in the inventive masterbatch, formulation, and/or productat from 0.001 to 0.2 wt%, alternatively 0.01%, alternatively 0.01 to0.10 wt%, all based on total weight thereof.

Optional constituent (additive) (I) (unsaturated carbon-carbonbond)-free hydrolyzable silane. Useful for scavenging moisture.Constituent (I) may be any monosilane containing at least 1,alternatively at least 2, alternatively at least 3, alternatively 4hydrolyzable groups (e.g., R² as defined above); and at most 3,alternatively at most 2, alternatively at most 1, alternatively 0non-hydrolyzable (unsaturated carbon-carbon bond)-free groups such asalkyl or aryl groups. Examples of (I) are acetoxytrimethylsilane,4-benzylphenylsulfonoxytributylsilane,dimethylamino-methoxy-dioctylsilane, octyltrimethoxysilane, andtetramethoxysilane. In some aspects (I) is not present in the inventivemasterbatch, formulation, and/or product. In some aspects (I) is presentin the inventive masterbatch, formulation, and/or product at from 0.1 to2 wt%, alternatively 0.1 to 1.5 wt%, alternatively 0.1 to 1.0 wt%; allbased on total weight thereof.

Optional constituent (additive) (J) a corrosion inhibitor. E.g., tin(II) sulfate. In some aspects (J) is not present in the inventivemasterbatch, formulation, and/or product. In some aspects (J) is presentin the inventive masterbatch, formulation, and/or product at from0.00001 to y, alternatively 0.0001%, based on total weight thereof.

Optional constituent (additive) (K) hindered amine light stabilizer. The(K) is a compound that inhibits oxidative degradation. Examples ofsuitable (K) are butanedioic acid dimethyl ester, polymer with4-hydroxy-2,2,6,6-tetramethyl-1-piperidine-ethanol (CAS No. 65447-77-0,commercially LOWILITE 62); andpoly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]) (CAS71878-19-8/70624-18-9, Chimassorb 994 LD, BASF). In some aspects (K) isnot present in the inventive masterbatch, formulation, and/or product.In some aspects (K) is present in the inventive masterbatch,formulation, and/or product at from 0.001 to 0.2 wt%, alternatively 0.01to 0.15 wt%, alternatively 0.01 to 0.10 wt%, all based on total weightthereof.

Optional constituent (additive) (L) ethylene-based copolymer additive.The constituent (L) is different than constituents (A) and (C). (L) isan LDPE, an ethylene/alpha-olefin copolymer, an ethylene/unsaturatedcarboxylic ester copolymer (e.g., ethylene/vinyl acetate (EVA)copolymer, ethylene/ethyl acrylate (EEA) copolymer, or ethylene/ethylmethacrylate (EEMA) copolymer). In some aspects (L) is not present inthe inventive masterbatch, formulation, and/or product. In some aspects(L) is present in the inventive masterbatch, formulation, and/or productat a concentration from 0.1 to 20 wt%, alternatively 1 to 10 wt%; andalternatively 5 to 20 wt%; all based on total weight thereof.

Other optional constituents. In some aspects the inventive masterbatch,formulation, and/or product does not contain any optional constituents.In some aspects the inventive masterbatch, formulation, and/or productdoes not contain any optional constituents other than constituents (D)to (L). In some aspects the inventive masterbatch, formulation, and/orproduct further contains at least one optional constituent (additive) inaddition to or in place of (D) to (L). For example, a lubricant or ananti-blocking agent.

Any optional constituent may be useful for imparting at least onecharacteristic or property to the inventive masterbatch, formulation,and/or product in need thereof. The characteristic or property may beuseful for improving performance of the inventive masterbatch,formulation, and/or product in operations or applications wherein theinventive masterbatch, formulation, and/or product is exposed toelevated operating temperature. Such operations or applications includemelt mixing, extrusion, molding, hot water pipe, and insulation layer ofan electrical power cable.

(C₃-C₂₀)alpha-olefin and (C₃-C₂₀)alpha-olefin. A compound of formula(I)— H₂C═C(H)—R (I), wherein R is either a straight chain (C₁-C₁₈)alkylgroup or a straight chain (C₂-C₁₈)alkyl group, respectively. The(C₃)alpha-olefin is 1-propene and its R group in formula (I) is methyl.The (C₂-C₁₈)alkyl group is a monovalent unsubstituted saturatedhydrocarbon having from 2 to 18 carbon atoms. Examples of (C₂-C₁₈)alkylare ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, and octadecyl. In some embodiments the (C₄-C₂₀)alpha-olefinis 1-butene, 1-hexene, or 1-octene; alternatively 1-butene, 1-hexene, or1-octene; alternatively 1-butene or 1-hexene; alternatively 1-butene or1-octene; alternatively 1-hexene or 1-octene; alternatively 1-butene;alternatively 1-hexene; alternatively 1-octene; alternatively acombination of any two of 1-butene, 1-hexene, and 1-octene.

Any compound herein includes all its isotopic forms, including naturalabundance forms and/or isotopically-enriched forms, which may haveadditional uses, such as medical or anti-counterfeiting applications.

Method of electron-beam irradiation curing. The method may compriseelectron-beam irradiating the EBC formulation with an effective dose ofelectron-beam irradiation. The effective dose of electron-beamirradiation may be from 49 to 201 kilojoules energy per kilogram of EBCformulation (kJ/kg), alternatively from 49 to 160 kJ/kg, alternativelyfrom 80 to 201 kJ/kg, alternatively from 80 to 160 kJ/kg, alternativelyfrom 50 to 80 kJ/kg, alternatively from 100 to 140 kJ/kg, alternativelyfrom 160 to 201 kJ/kg. The electron-beam irradiation may be producedusing an E-beam accelerator machine such as an Aibang AB5.0 machineavailable from Wuxi Aibang Radiation Technology Company, Limited,People’s Republic of China. The electron-beam irradiating step may beconducted at any suitable temperature such as from 10 ° to 50° C. (e.g.,23° C. ± 1° C.), under any suitable atmosphere such as air or molecularnitrogen gas, and for any suitable length of time such as from 0.1 to 20minutes, alternatively from 0.1 to 10 minutes, alternatively from 0.1 to5 minutes. The irradiation may be dosed continuously or intermittently,alternatively continuously.

The following apply unless indicated otherwise. Alternatively precedes adistinct embodiment. ASTM means the standards organization, ASTMInternational, West Conshohocken, Pennsylvania, USA. IEC means thestandards organization, International Electrotechnical Commission,Geneva, Switzerland. Any comparative example is used for illustrationpurposes only and shall not be prior art. Free of or lacks means acomplete absence of; alternatively not detectable. IUPAC isInternational Union of Pure and Applied Chemistry (IUPAC Secretariat,Research Triangle Park, North Carolina, USA). May confers a permittedchoice, not an imperative. Operative means functionally capable oreffective. Optional(ly) means is absent (or excluded), alternatively ispresent (or included). PPM are weight based. Properties are measuredusing a standard test method and conditions for the measuring (e.g.,viscosity: 23° C. and 101.3 kPa). Ranges include endpoints, subranges,and whole and/or fractional values subsumed therein, except a range ofintegers does not include fractional values. Room temperature is 23° C.± 1° C. Substituted when referring to a compound means having, in placeof hydrogen, one or more substituents, up to and including persubstitution. Comonomer composition distribution may be characterized bythe CDBI Method.

Comonomer Distribution Breadth Index (CDBI) Method: Methods forcalculating CDBI values of copolymers are known in the art, such as inWO 93/03093. A CDBI value of a copolymer is readily calculated by dataobtained from techniques known in the art, such as, for example, TREF(temperature rising elution fractionation) as described, for example, inUS 5,008,204 or in Wild et al., J. Poly. Sci. Polv. Phys. Ed., vol. 20,p. 441 (1982). The CDBI Method is as described in paragraphs [0054] to[0061] of U.S. Provisional Pat. Application No. 62/478,163 filed Mar.29, 2017, and its corresponding PCT International patent applicationnumber PCT/US2018/______ filed March______, 2018.

Crystallinity Test Method. For determining crystallinity in wt% of asemi-crystalline polyolefin resin such as (A) semi-crystallinepolyolefin carrier resin. Determine melting peaks and weight percent(wt%) crystallinity using DSC instrument DSC Q1000 (TA Instruments) asfollows. Procedure (A) Baseline calibrate instrument. Use softwarecalibration wizard. First obtain a baseline by heating a cell from -80 °to 280° C. without any sample in an aluminum DSC pan. Then use sapphirestandards as instructed by the calibration wizard. The analyze 1 to 2milligrams (mg) of a fresh indium sample by heating the standards sampleto 180° C., cooling to 120° C. at a cooling rate of 10° C./minute, thenkeeping the standards sample isothermally at 120° C. for 1 minute,followed by heating the standards sample from 120 ° to 180° C. at aheating rate of 10° C./minute. Determine that indium standards samplehas heat of fusion (H_(f)) = 28.71 ± 0.50 Joules per gram (J/g) andonset of melting = 156.6 ° ± 0.5° C. Perform DSC measurements on testsamples using same DSC instrument. For polyethylene test samples seeprocedure (B) below. For polypropylene test samples see procedure (C)below. Weight percent crystallinity values determined using DSC will beapproximately 3 wt% lower than weight percent crystallinity valuesdetermined according to a method based on density of thesemi-crystalline polyolefin.

Procedure (B) DSC on Polyethylene Test Samples. Press test sample ofpolymer into a thin film at a temperature of 160° C. Weigh 5 to 8 mg oftest sample film in DSC pan. Crimp lid on pan to seal pan and ensureclosed atmosphere. Place sealed pan in DSC cell, equilibrate cell at 30°C., and heat at a rate of about 100° C./minute to 140° C., keep sampleat 140° C. for 1 minute, cool sample at a rate of 10° C./minute to 0° C.or lower (e.g., -40° C.) to obtain a cool curve heat of fusion (H_(f)),and keep isothermally at 0° C. or lower (e.g., -40° C.) for 3 minutes.Then heat sample again at a rate of 10° C./minute to 180° C. to obtain asecond heating curve heat of fusion (ΔH_(f)). Using the resultingcurves, calculate the cool curve heat of fusion (J/g) by integratingfrom the beginning of crystallization to 10° C. Calculate the secondheating curve heat of fusion (J/g) by integrating from 10° C. to the endof melting. Measure weight percent crystallinity (wt% crystallinity) ofthe polymer from the test sample’s second heating curve heat of fusion(ΔH_(f)) and its normalization to the heat of fusion of 100% crystallinepolyethylene, where wt% crystallinity = (ΔH_(f)*100%)/292 J/g, whereinΔH_(f) is as defined above, * indicates mathematical multiplication, /indicates mathematical division, and 292 J/g is a literature value ofheat of fusion (ΔH_(f)) for a 100% crystalline polyethylene.

Procedure (C) DSC on Polypropylene Test Samples. Press test sample ofpolypropylene into a thin film at a temperature of 210° C. Weigh 5 to 8mg of test sample film in DSC pan. Crimp lid on pan to seal pan andensure closed atmosphere. Place sealed pan in DSC cell and heat at arate of about 100° C./minute to 230° C., keep sample at 230° C. for 5minutes, cool sample at a rate of 10° C./minute to -20° C. to obtain acool curve heat of fusion, and keep isothermally at -20° C. for 5minutes. Then heat sample again at a rate of 10° C./minute until meltingis complete to obtain a second heating curve heat of fusion ((ΔH_(f))).Using the resulting curves, calculate the cool curve heat of fusion(J/g) by integrating from the beginning of crystallization to 10° C.Calculate the second heating curve heat of fusion (J/g) by integratingfrom 10° C. to the end of melting. Measure weight percent crystallinity(wt% crystallinity) of the polymer from the test sample’s second heatingcurve heat of fusion (ΔH_(f)) and its normalization to the heat offusion of 100% crystalline polypropylene, where wt% crystallinity =(ΔH_(f)*100%)/165 J/g, wherein ΔH_(f) is as defined above, * indicatesmathematical multiplication, / indicates mathematical division, and 165J/g is a literature value of heat of fusion_(ΔH_(f)) for a 100%crystalline polypropylene.

Density Test Method: measured according to ASTM D792-13, Standard TestMethods for Density and Specific Gravity (Relative Density) of Plasticsby Displacement, Method B (for testing solid plastics in liquids otherthan water, e.g., in liquid 2-propanol). Report results in units ofgrams per cubic centimeter (g/cm³).

Hot Creep (Hot Set) Test Method: A test sample (dog-bone-shaped ofspecified dimensions in ASTM 638-34; thickness < 2 millimeter (mm);marker lines 20 mm apart) is placed in an oven at 200° C., and to thetest sample is attached a weight equal to a force of 20 Newtons persquare centimeter (N/cm²). Elongation of the test sample (distancebetween marker lines) under these conditions is then measured, andexpressed as a percentage of the initial 20 mm distance. To illustrate,if the distance between marker lines widens to 40 mm, the hot creep is100% (100 * (40-20)/20) = 100%), if widens to 100 mm, the hot creep is400%. All other things being equal, the lower the level of crosslinkingin the test sample, the greater the extent of elongation thereof in theHot Creep Test Method. Conversely, the higher the level of crosslinkingin the test sample, the lesser the extent of elongation thereof. If thelevel of crosslinking in the test sample is low enough, the test samplecan fail by breaking, which may occur within a few minutes or evenseconds of start of its testing run. Although power cables may notexperience operating temperatures as high as 200° C., this test is areliable way for the industry to evaluate materials for use ininsulation layers thereof. The lower the hot creep percent, the betterthe performance of the material. In the power cable industry, a hotcreep of less than 175% after the test sample has been held for 15minutes at 200° C. passes the hot creep test. And a hot creep of lessthan 100% after 15 minutes at 200° C. is especially desirable. If thetest sample is intact after 15 minutes, the weight is removed, the testsample is removed from the oven and allowed to cool to room temperature.Residual elongation of the test sample after cooling is measured. For apower cable, the residual elongation at room temperature should be lessthan 15% of the hot creep value measured at 200° C.

Melt Flow Rate (230° C., 2.16 kilograms (kg), “MFR”) Test Method: forpropylene-based (co)polymer is measured according to ASTM D1238-13,using conditions of 230° C./2.16 kg, formerly known as “Condition E” andalso known as MFR. Report results in units of grams eluted per 10minutes (g/10 min.) or the equivalent in decigrams per 1.0 minute (dg/1min.). 10.0 dg = 1.00 g.

Melt Index (190° C., 2.16 kilograms (kg), “I₂”) Test Method: forethylene-based (co)polymer is measured according to ASTM D1238-13, usingconditions of 190° C./2.16 kg, formerly known as “Condition E” and alsoknown as I₂. Report results in units of grams eluted per 10 minutes(g/10 min.) or the equivalent in decigrams per 1.0 minute (dg/1 min.).10.0 dg = 1.00 g.

Sweat Out Test Method (Qualitative): prepare HDPE pellets containingcoagent as described later for the inventive masterbatch examples (e.g.,IE1 to IE4). Prepare LLDPE pellets containing coagent as described laterfor comparative EBC formulations CE1 to CE5. Add each pellets sample toa separate, unused press-sealed polyethylene plastic bag (also known aszip lock or click seal bags). Seal bags. Press pellets in bags. Storebags and contents at room temperature for 14 days. At 14 days observebags for oil traces left over on the bags’ surfaces under light. Oiltrace indicates surface migration and poor solubility. More oil trace onsurface of bag, more TAIC sweat-out. Rank progressive amount of sweatout by characterizing the oil trace as none, very little, little, orobvious (more than a little).

Sweat Out Test Method (Quantitative): prepare HDPE pellets or LLDPEpellets as described above for the qualitative test method. Usingthermogravimetric analysis (TGA) measure the initial loading of coagenton a freshly prepared pellet. Each pellet weighs 20 to 30 mg and isapproximately dimensioned 4 mm x 2.5 mm in volume. Store the pellets for20 days at room temperature. At 20 days, wash a sample of the storedpellets with acetonitrile (ACN) as per the following procedure: (1)weigh 3.000 g ± 0.001 g of pellets sample into a 40 mL vial. (2) Feed14.5 mL of ACN into the 40 mL vial. (3) Seal the vial with arubber-lined cap, and shake the sealed vial on a shaker for 5 minutes.After shaking analyze the washed pellets sample by TGA again to get thecoagent content in the washed pellets. Calculate the percent reductionof coagent content in the washed pellets by comparing the initialcoagent loading in the fresh pellet to the coagent content in the washedpellet. Quantify the percent migration of coagent in the HDPE or LLDPEcompound as equal to the coagent content reduction (%) of the pelletsafter the storage.

EXAMPLES

Semi-crystalline polyolefin carrier resin (A1): a HDPE having a densityof 0.965 g/cc³, a melt index (I₂) of 7.5 to 8.5 g/10 min.; and amonomodal MWD. By the Crystallinity Test Method parts (A) and (B), resin(A1) had a second heating curve heat of fusion (ΔH_(f)) of 223.7 J/g,and a corresponding crystallinity of 76.6 wt%. Available as productAXELERON™ CX 6944 NT CPD from The Dow Chemical Company.

Alkylene-functional coagent (B1): triallyl isocyanurate (TAIC).

Alkenyl-functional coagent (B2):tetramethyl-tetravinyl-cyclotetrasiloxane (ViD4).

Alkenyl-functional coagent (B3): trimethylolpropane trimethylacrylate(“TMPTMA”).

Alkenyl-functional coagent (B4): triallyl cyanurate (TAC).

EBC polyolefin compound (C1): an ethylene/1-butene LLDPE (C1),stabilized with metal deactivator (H1) oxaylyl bis(benzylidene hydrazide(OABH) and two antioxidants, and has a density of 0.921 g/cc³, meltindex (I₂) of 0.7 g/10 min., and a monomodal MWD. Available as pelletsas product DFDA-7540 NT from The Dow Chemical Company.

Comparative Examples 1 and 2 (CE1 and CE2): two comparative EBCformulations are prepared by soaking LLDPE (C1) pellets with one ofcoagent (B1) 80º C. for 6 hours in an oven to allow coagent to penetrateinto the LLDPE pellets.

Comparative Examples 3 to 5 (CE3 to CE5): three comparative EBCformulations are prepared separately by compounding. Feed LLDPE (C1) toa Brabender mixer at 120° C. Allow the LLDPE (C1) to melt completely ata rotor speed of 35 rotations per minute (rpm). Then gradually add oneof coagents (B2) to (B4), respectively, over 15 minutes, and melt mixthe resulting mixture at 35 rpm for 4 minutes. Then stop the rotation,remove the mixed EBC formulation (one of CE3 to CE5) from the Brabendermixer. Promptly hot press the formulation at 120° C. to shape theformulation CE3, CE4, or CE5 as a 1-millimeter (mm) thick sheet.

Comparative Examples 6 and 7: comparative cured polyolefin productsprepared by separately hot pressing the formulation CE1 or CE2 at 120°C. to shape the formulation CE1 or CE2 as a 1-mm thick sheet, and thencuring the sheet EBC formulations of CE1 and CE2, respectively, with 100kilojoules per kilogram (kJ/kg) irradiation dose of electron-beam.

Inventive Examples 1 to 4 (IE1 to IE4): inventive coagent masterbatchesMB1 to MB4. Melt mix HDPE (A1) and any one of coagents (B1) to (B4) in aBanbury compounder using a compounding temperature of 155° C., rotorspeed of 60 to 65 rotations per minute (rpm), followed by extruding themelt of coagent masterbatch with air cooling to give extruded coagentmasterbatch, and pelletizing the extruded coagent masterbatch to givecoagent masterbatch of IE1 to IE4 as pellets.

Inventive Examples 5 to 6: inventive EBC formulations EBCF1 to EBCF2.

Inventive Examples 7 and 8: inventive cured polyolefin products preparedby curing the EBC formulations EBCF1 and EBCF2 of IE5 and IE6,respectively, with 100 kilojoules per kilogram (kJ/kg) irradiation doseof electron-beam.

See Table 1 later for composition information for comparative EBCformulations CE1 to CE5. See Table 2 later for composition informationfor masterbatches MB1 to MB4 of IE1 to IE4. See Table 3 later forcomposition information for inventive EBC formulations EBCF1 to EBCF2 ofIE5 to IE6. See Table 4 later for sweat out results for CE1 to CE5. SeeTable 5 later for sweat out results for IE1 to IE6. See Table 6 laterfor hot creep test results for CE6 and CE7 and IE7 and IE8.

TABLE 1 Compositions (wt%): Comparative EBC Formulations CE1 to CE5. Ex.No. CE1 CE2 CE3 CE4 CE5 HDPE (A1) 0 0 0 0 0 TAIC (B1) 0.5 0.8 0 0 0 ViD4(B2) 0 0 13 0 0 TMPTMA (B3) 0 0 0 13 0 TAC (B4) 0 0 0 0 13 LLDPE (C1)99.5 99.2 87 87 87 Total 100.00 100.00 100.00 100.00 100.00 Coagent andLoading (wt%) TAIC (0.5) TAIC (0.8) ViD4 (13) TMPTMA (13) TAC (13)

TABLE 2 Compositions (wt%): Inventive Coagent Masterbatches MB1 to MB4of IE1 to IE4, respectively. Ex. No. IE1 IE2 IE3 IE4 HDPE (A1) 85 87 8787 TAIC (B1) 15 0 0 0 ViD4 (B2) 0 13 0 0 TMPTMA (B3) 0 0 13 0 TAC (B4) 00 0 13 Masterbatch Total wt% 100.00 100.00 100.00 100.00

TABLE 3 Compositions (wt%): Inventive EBC Formulations EBCF1 to EBCF2made with inventive Coagent Masterbatches MB1. Ex. No. IE5 IE6 MB1 (IE1)8 40 MB2 (IE2) 0 0 MB3 (IE3) 0 0 MB4 (IE4) 0 0 LLDPE (C1) 92 60 EBCFormulation Total 100.00 100.00 Coagent and loading (wt%) TAIC (1.2)TAIC (6)

TABLE 4 Sweat out Results for Comparative EBC Formulations CE1 to CE5.Ex. No. CE1 CE2 CE3 CE4 CE5 Test Material EBC Formulation EBCFormulation EBC Formulation EBC Formulation EBC Formulation Sweat Outamount coagent lost Very little Yes, obvious > 5% > 50% > 10% Sweat OutTest Method Qualitative Qualitative Quantitative QuantitativeQuantitative

TABLE 5 Sweat out Results for Inventive EBC Formulations EBCF1 to EBCF2and inventive Coagent Masterbatches MB2 to MB4. Ex. No. IE2 IE3 IE4 IE5IE6 Test Material MB2 MB3 MB4 EBCF1 EBCF2 Sweat Out amount coagent lost(test period) 0% 0% 0% None None Sweat Out Test Method QuantitativeQuantitative Quantitative Qualitative Qualitative

The sweat out data in Tables 4 and 5 show that the inventive coagentmasterbatch is significantly better and preventing sweat out ofalkenyl-functional coagent therefrom at room temperature than is anLLDPE/coagent mixture.

TABLE 6 Hot Creep Results for comparative cured polyolefin products CE6and CE7 and inventive cured polyolefin products IE7 and IE8. Ex. No. CE6CE7 IE7 IE8 Pre-cure TAIC loading in EBC Formulation (wt%) 0.5 0.8 1.2 6Cured* Test Material Product of curing EBC Formulation of CE1 Product ofcuring EBC Formulation of CE2 Product of curing EBCF1 Product of curingEBCF2 Hot Creep** 250% 150% 80% 35% Hot Creep < 175%? Fail pass PassPass Hot Creep < 100%? Fail Fail Pass Pass *curing=100 kilojoules perkilogram (kJ/kg) irradiation dose of electron-beam irradiation; **HotCreep: measured at 200° C. on electron-beam cured test material.

The hot creep data in Table 6 show that the inventive EBC formulations,which contain the inventive masterbatch, are significantly better atcuring to give inventive cured polyolefin products having improved(decreased) hot creep at 200° C. than are comparative cured polyolefinproducts prepared from comparative EBC formulations that contain thesame alkenyl-functional coagent but do not contain the inventivemasterbatch. The TAIC loading in the comparative EBC formulations islower due to TAIC sweat out limits than is the TAIC loading in theinventive EBC formulations, which do not have such sweat out limits. Thehigher TAIC loading in the inventive EBC formulations show thebeneficial effect of increasing electron-beam curing efficiency of theinventive curing method.

1-14. (canceled)
 15. An (electron beam)-curable formulation comprising acoagent masterbatch and (C) an electron-beam curable (EBC) polyolefincompound; wherein the coagent masterbatch comprises (A) asemi-crystalline polyolefin carrier resin and (B) an alkylene-functionalcoagent disposed in the (A) semi-crystalline polyolefin carrier resin;wherein (A) is 80.0 to 99.9 weight percent (wt%) and (B) is from 20.0 to0.1 wt% of the combined weight of constituents (A) and (B); wherein the(A) semi-crystalline polyolefin carrier resin has a crystallinity offrom 55.0 to less than 100 weight percent (wt%) as measured byCrystallinity Test Method using differential scanning calorimetry (DSC);wherein when the (A) semi-crystalline polyolefin carrier resin is asemi-crystalline polyethylene, the semi-crystalline polyethylene has adensity of greater than 0.935 gram per cubic centimeter (g/cm³); whereinthe (electron beam)-curable formulation is free of a peroxide.
 16. The(electron beam)-curable formulation of claim 15 wherein the (A)semi-crystalline polyolefin carrier resin comprises any one of (i) to(viii): (i) a semi-crystalline medium density polyethylene; (ii) asemi-crystalline high density polyethylene; (iii) a semi-crystallinepolypropylene; (iv) a semi-crystalline ethylene/propylene copolymer; (v)a semi-crystalline poly(ethylene-co-alpha-olefin) copolymer; (vi) acombination of any two or more of (i), (ii) and (v); (vii) the (A)semi-crystalline polyolefin carrier resin has a crystallinity of 57.5 to< 100 wt% (Crystallinity Test Method using DSC); or (viii) limitation(vii) and any one of limitations (i) to (vi).
 17. The (electronbeam)-curable formulation of claim 15 wherein the (A) semi-crystallinepolyolefin carrier resin has any one of (i) to (viii): (i) a density ofgreater than 0.936 g/cm³ and is a polyethylene; (ii) a density of 0.89to 0.946 g/cm³ and is a polypropylene; (iii) a crystallinity of 60.0 to< 100 wt% (Crystallinity Test Method using DSC) and is a polyethylene;(iv) a melt index (I₂, 190° C./2.16 kg load) of 0.1 to 20 grams per 10minutes (g/10 min.) measured according to the Melt Index Test Method andis a polyethylene or a melt flow rate (MFR) of 0.5 to 20 g/10 min. (230°C./2.16 kg load) measured according to the Melt Flow Rate Test Methodand is a polypropylene; (v) a molecular weight distribution (MWD) thatis monomodal; (vi) a MWD that is multimodal; (vii) wherein the combinedweight of constituents (A) and (B) is from 50 to 100 wt% of the coagentmasterbatch; (viii) any two or limitations (i) to (vii).
 18. The(electron beam)-curable formulation of claim 15 wherein the (B)alkenyl-functional coagent is as described by any one of limitations (i)to (viii): (i) (B) is 2-allylphenyl allyl ether;4-isopropenyl-2,6-dimethylphenyl allyl ether; 2,6-dimethyl-4-allylphenylallyl ether; 2-methoxy-4-allylphenyl allyl ether; 2,2′-diallyl bisphenolA; O,O′-diallyl bisphenol A; or tetramethyl diallylbisphenol A; (ii) (B)is 2,4-diphenyl-4-methyl-1-pentene or 1,3-diisopropenylbenzene; (iii)(B) is triallyl isocyanurate; triallyl cyanurate; triallyl trimellitate;N,N,N′,N′,N″,N″-hexaallyl-1,3,5-triazine-2,4,6-triamine; triallylorthoformate; pentaerythritol triallyl ether; triallyl citrate; ortriallyl aconitate; (iv) (B) is trimethylolpropane triacrylate,trimethylolpropane trimethylacrylate, ethoxylated bisphenol Adimethacrylate, 1,6-hexanediol diacrylate, pentaerythritoltetraacrylate, dipentaerythritol pentaacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, or propoxylated glyceryl triacrylate; (v) (B)is a polybutadiene having at least 50 wt% 1,2-vinyl content or trivinylcyclohexane; (vi) (B) is an alkenyl-functional organosiloxane of formula(I): [R¹,R^²iO_(2/2]n) (I), wherein subscript n is an integer greaterthan or equal to 3; each R¹ is independently a (C₂-C₄)alkenyl or aH₂C═C(R^(1a))—C(═O)—O—(CH₂)_(m)—wherein R^(1a) is H or methyl andsubscript m is an integer from 1 to 4; and each R² is independently H,(C₁-C₄)alkyl, phenyl, or R¹; (vii) (B) is an alkenyl-functionalmonocyclic organosiloxane of formula (II): (R¹)_(x)Si(OR²) (_(4-x))(II), wherein subscript x is an integer from 0 to 4; each R¹ isindependently a (C₂-C₄)alkenyl or a H₂C═C(R^(1a))—C(═O)—O—(C^(H)2)m—wherein R^(1a) is H or methyl and subscript m is an integer from 1 to 4;and each R² is independently H, (C₁-C₄)alkyl, phenyl, or R¹; with theproviso that the alkenyl-functional monocyclic organosiloxane of formula(II) contains from 2 to 4 R¹ groups; (viii) a combination or any two ormore of (i) to (vii).
 19. The (electron beam)-curable formulation ofclaim 15 characterized by any one of limitations (i) to (xiii): (i) the(C) EBC polyolefin compound is a low density polyethylene (LDPE) havinga density from 0.910 to 0.925 g/cm³; (ii) the (C) EBC polyolefincompound is a linear low density polyethylene (LLDPE) having a densityfrom 0.910 to 0.925 g/cm³; (iii) the (C) EBC polyolefin compound is amedium density polyethylene (MDPE) having a density from 0.926 to 0.940g/cm³; (iv) the (C) EBC polyolefin compound is a high densitypolyethylene (HDPE) having a density from 0.941 to 0.990 g/cm³; (v) the(C) EBC polyolefin compound is a polyethylene elastomer selected from anethylene-propylene rubber (EPR), ethylene-1-butene rubber (EBR), andethylene-1-octene rubber (EOR); (vi) the (C) EBC polyolefin compound isan ethylene/(C₃-C₂₀)alpha-olefin) copolymer; (vii) the (C) EBCpolyolefin compound is an ethylene-propylene copolymer (EPP); (viii) the(C) EBC polyolefin compound is an ethylene-propylene-diene monomer(EPDM) copolymer; (ix) the (C) EBC polyolefin compound is a combinationof any two or more of (i) to (viii); (x) the (electron beam)-curableformulation further comprises at least one additive that is not aconstituent of the coagent masterbatch and is independently selectedfrom optional additives (D) to (L): (D) a flame retardant, (E) anantioxidant, (F) a processing aid, (G) a colorant, (H) a metaldeactivator, (I) an (unsaturated carbon-carbon bond)-free hydrolyzablesilane, (J) a corrosion inhibitor, (K) a hindered amine lightstabilizer, and (L) an ethylene-based copolymer additive that isdifferent than constituents (A) and (C) and is anethylene/(C₄-C₂₀)alpha-olefin copolymer, an ethylene/unsaturatedcarboxylic ester copolymer, or a propylene/ethylene-based copolymer;(xi) limitation (x) and any one of limitations (i) to (viii); (xii) (B)is from 0.1 to 20 wt% of the combined weight of constituents (A), (B)and (C); and (xiii) limitation (xii) and any one of limitations (i) to(xi).
 20. A method of making an (electron beam)-curable formulation ofclaim 15, the method comprising mixing together a divided solid form ofthe coagent masterbatch and the (C) EBC polyolefin compound in dividedsolid or melt form so as to give a mixture; and melt mixing or extrudingthe mixture so as to make the (electron beam)-curable (EBC) formulation.21. A method of electron-beam curing a formulation in need thereof, themethod comprising irradiating the EBC formulation of claim 15 with aneffective dose of electron-beam irradiation so as to give anelectron-beam cured polyolefin product.
 22. An electron-beam-curedpolyolefin product made by the method of claim
 21. 23. A manufacturedarticle comprising the electron-beam-cured polyolefin product of claim22 and a component in operative contact therewith.
 24. A coatedconductor comprising a conductive core and a polymeric layer at leastpartially surrounding the conductive core, wherein at least a portion ofthe polymeric layer comprises the electron-beam-cured polyolefin productof claim
 22. 25. A method of conducting electricity, the methodcomprising applying a voltage across the conductive core of the coatedconductor of claim 24 so as to generate a flow of electricity throughthe conductive core.